A new class of optically active, monodentate, C-3-symmetric Ligands for asy
mmetric catalysis, 1-3, were prepared via routes involving asymmetric reduc
tion of aryl ketones (Schemes 1-3). Single crystal X-ray structures of tran
s-PdCl2(phosphine)(2) complexes of Ligands 1a, 2a and 3a showed that the li
gands do not adopt perfect C3-symmetric conformations in the solid state; i
n fact, all three have one aromatic ring lying 'face-on' to the metal. Circ
ular dichroism studies of the same complexes provided some evidence for an
aromatic ordering effect for complex 22, but none for 21 and 23. Palladium
catalyzed allylation reactions using ligands 1-3 showed that encouraging en
antioselectivities could be obtained, particularly for cyclic, allylic subs
trates. (C) 2001 Elsevier Science Ltd. All rights reserved.